Method of producing butene-1

ABSTRACT

The present invention relates to a method of producing butene-1. According to the invention, the method of producing butene-1 resides in dimerizing ethylene in the presence of a complex organometallic catalyst of the formula (RO)3TiR&#39;&#39;.AlR2&#39;&#39;&#39;&#39;OR + AlR2&#39;&#39;&#39;&#39;R&#39;&#39;, where R is an alkyl radical with the number of carbon atoms from 2 to 4, R&#39;&#39; R or H, R&#39;&#39;&#39;&#39; is the same as R, or of a catalyst of the formula Ti(OR)4 + AlR2&#39;&#39;&#39;&#39;R&#39;&#39; and modifiers such as (C5H5)2TiCl2, oxygen, metaphenylenediamine or N-phenyl- Beta naphthylamine, in the medium of solvents such as n-heptane, ndecane, toluene, diethyl ether, ethyl chloride, vinylbutyl ether, tetrahydrofuran, diphenyl ether, methylphenyl ether and their mixtures. The invention will find application in petrochemical processing.

United States Patent 1W1 Belov et a1.

1 1 METHOD OF PRODUCING BUTENE-l [76] Inventors: Gennady PetroviehBelov. Noginsky raion, p/o Chernogolovku, ulitsa Pervaya, 5, kv, l5;Taimuraz Savelievich Dzhabiev, Noginsky raion, p/o Chernogolovkai,ulits'ti Pervaya, 31, kv. 41; Fridrikh Stepanovich Dyachkovsky. Noginskyruion, p/o Chernogolovku, ulitsa Tretya, 3, kv. 2; Vyacheslav lvanovichSmirnov, Noginsky ruion, p/o Chernogolovka, ulitsa Tretya, l. kv l9;Nelli Dzhavkharovna Karpova, Noginsky rziion, p/o Chernogolovka, ulitsaPervaya, 29, kv. 100; Khaim-Mordkhe Aronovich Brikenshtein, Noginskyraion, p/o Chernogolovka, ulitsa Vtoraya, 5, kv. l; Matrena PetrovnaGerasina, Noginsky raion, p/o Chernogolovku, ulitsa Pervaya, 2a, kv. 61,all of Moskovskaya oblast: Vladimir Evgenievich Kuzmin, ulitsa 50letiyii Oktyabrya, 13/12, kv, 199, Kazan; Petr Evgenievich Matkovsky,Noginsky raion, p10 Chernogolovka, ulitsa Pervaya, l6, kvv 26,Moskovskaya oblust; Ljudmila Nikolaevna Russiyan. Noginsky raion, p/oChernogalovka. ulitsa Pervaya, 2a, kv. 41, Moskovskuya oblast; Anatoly[)mitrievich Pomogailc, Noginsky raion, p/o Chernogolovku, ulitsaPervaya, 33, kv. l5, Moskovskuya ohlast, all of USSR, NikolaiMikhailovieh Chirkov, deceased, late of Moscow, U S,S,R,; by MikhailNikolaevich Chirkov, administrator, ulitsa Vuvilovu. 55/5, kv. 6,Moscow, USSR.

1 1 Get. 7, 1975 221 Filed: Aug. 5, 1974 [21] App1.No.:494,9l7

Related US. Application Data [62] Division of Ser. No. 436,809, Jan. 25,1974,

0.5. CI 260/683.l5 D Int. Cl. l. CO'I'C 3/10 Field of Search l.IMO/(183.15 D

[56] References Cited UNITED STATES PATENTS 2,907,805 10/1959 Bestian eta1, 260/(183.15 D 2,943,125 6/1960 Ziegler et al 260/683.15 D 3,564,0712/1971 lzziwa et a1 EGO/683.15 D 3,686,350 8/1972 Ono et a1. 260/68315 DPrimary ExuminerPaul M. Coughlan, Jr. Attorney, Agenl, or FirmH0lman &Stern [57] ABSTRACT The present invention relates to a method ofproducing butene-l.

According to the invention, the method of producing butenel resides indimerizing ethylene in the presence of a complex organometallic catalystof the formula (ROMTiRKAlRf'OR AlR "R', where R is an alkyl radical withthe number ofcarbon atoms from 2 to 4, R R or H, R is the same as R, orof ll catalyst of the formula THOR), i AlR "R and modifiers such as (C HTiCl oxygen. metaphenylenediamine or N-phenyl-B-nuphthylzimine, in themedium of solvents such as n-heptane. n-decane, toluene, diethyl ether,ethyl chloride, vinylbutyl ether, tetrahydrofuran, diphenyl ether,methylphenyl ether and their mixtures.

The invention will find application in petrochemical processing 1 Claim,N0 Drawings METHOD OF PRODUCING BUTENE-l This is a divisional ofapplication Ser. No. 436,809, filed Jan. 25, 1974.

The present invention relates to the field of producing unsaturatedhydrocarbons. and more particularly to methods of producing butene-l.

Butene-l can be used in the production of n-butyl alcohol, copolymers ofethylene with butylene, isotactic polybutene, butylene oligomers, aswell as in the production of butadiene and other products ofpetrochemical processing.

Several methods of producing butenc-l are known in the art: separationof butenc-l from the butanebutylene fraction of cracked gases,dehydration of butyl alcohol, dehydrogenation of butane, and thermal orcatalytic cimerization of ethylene.

The process of producing butene-l by dimerizing ethylene on complexorganometallic catalysts has gained wide acceptance. In accordance withthe known methods, dimerization of ethylene to butene-l is carried outat temperatures ranging from to lOOC, preferably from 10 to 40C, thepressure of ethylene being either atmospheric or elevated (up to 40gauge atmospheres), in the medium of organic solvents (heptane, hexane,benzene, toluene, butane, isooctane, or mixtures of these solvents withbutene-l In the processes of ethylene dimerization complex catalystsincluding compounds of nickel, cobalt or titanium are employed Catalystsbased on nickel or cobalt compounds are noted for their low selectivity.

Reactions of ethylene dimerization run on these catalysts give a complexmixture of products consisting of butene-l, cis-trans-butenes-Z,hexenes, octenes, etc. Dimerization of ethylene on catalysts consistingof titanium alkoxides and organoaluminium compounds (Ti- (OR), AIR, orAlR "H where R, R, R" stand for an alkyl, cycloalkyl or aryl hydrocarbonradical) in the medium of hydrocarbon solvents, usually results in theformation, alongside of butene-l, of 0.5 to 5.0 vol. per cent ofbutenes-2 and from L5 to 8.0 weight per cent of polyethyleneDimerization of ethylene on catalysts of this type with ethylenepressure of l to atm proceeds at a relatively low rate 1 to 2 g/lit permin. with the concentration of THOR), of about S'lO m0le/lit.). In thecourse of the process the catalyst rapidly loses its activ ity, whichresults in lowering of its capacity, i.e., in a lower yield of butene-lin moles per mole of Ti(OR),,.

With a view to increasing the activity and capacity of the catalyst, theprocess of dimerizing ethylene to butene-l is recommendable to becarried out at low temperatures (ranging from 10 to 40C), this involvingconsiderable difficulties as regards the problem of heat removal.

Lovv selectivity of the known processes of dimerizing ethylene tobutene-l, low yields of the desired product per unit weight of thecatalyst, sophisticated and cumbersome process equipment, all thesefactors are responsible for the high ultimate cost price of butene-l.This is to a considerable extent associated with the fact that theformation of by-products, even in small amounts (2 to 5 weight per centfor the reacted ethylene) adversely tells on the entire technologicalprocess of producing butcne-l. since by-products not only lower theyield of butene-l and its purity, but also reduce the working time ofthe process equipment, insofar as solid polymer accumulating in thereactors has to be periodically removed, which can be done only byinterrupting the dimerization process and, hence. at the expense of losttime of the equipment.

In some cases, for attaining partial improvement of processcharacteristics, it was suggested to introduce catalyst modifiers intothe reaction mixture in amounts commcnsurable with the amount of thecatalyst components (the molar ratio modifier/Ti(OR) being 0.0] to 10;modifier/AlR being 0.01 to 1.0).

As modifiers use is made of organic esters of orthophosphoric acid,diphenylamine, phenothiazine, etc.

The inclusion of these compounds into the composition of the catalyst inamounts of 0.l to 1.0 mole per mole of the taken alkylaluminium leads toa certain reduction in the polymer formation; however, the activity andcapacity of the catalyst are also essentially reduced in this case.

Different compounds used as modifiying additives, even if they belong tothe same class of compounds, produce different influence on both therate of dimerization of ethylene to butene-l and on side reactions ofpolymerization of ethylene to polyethylene. At present it is hardlypossible to establish any definite relation ship between the propertiesof the modifier (its struc ture, etc.) and the inhibitory effect itproduces on the reaction of polymer formation, or its general influenceon the process of dimerization of ethylene to butene-l It is just forthis reason that patents teach the applica tion as modifiers of onlyindividual compounds and not of whole classes of compounds.

It is an object of the present invention to increase the catalystactivity.

Another object of the invention is to enhance the se lectivity of theprocess by diminishing polymerization of ethylene to high-molecularpolyethylene, as well as to diminish the rate of or preclude theformation of bu tene-2 and higher olefines.

Said objects have been accomplished by the provision ofa method ofproducing butene-l residing in that dimerization of ethylene to butene-lis carried out, according to the invention, in the presence of a complexorganometallic catalyst consisting of titanium alcoholates of theformula (ROhTiR. AlR "OR and alkylaluminium of the formula AlR" R, whereR is an alkyl radical with the number of carbon atoms from 2 to 4, R=Ror H, R" is the same as R, in the medium of hydrocarbon solvents such asn-heptane, mdecane, toluene.

Titanium alcoholates of the formula (RO) TiR-AlR" OR contain ethoxy,propoxy-, isopropoxy butoxy-, isobutoxygroups linked with titanium andaluminium. As diand trialklaluminium of the formula AlR "R'triethylaluminium, tributylaluminium, triisobutylaluminium,diisobutylaluminium hydride, tripropylaluminium, ortriisopropylaluminium is used. Optimal results are obtained with thecatalyst of the formula (C,,H,,O);,Ti C H 'Al(C H,,) OC,H

Depending on particular conditions, the molar ratio of trialkylaluminiumto titanium alcoholate in the catalyst when carrying out dimerization ofethylene to butene-l is varied within a range of from 1.5 to I00. Theconcentration of titanium alcoholate in the reaction medium is variedwithin a range of from 1-10" to l'l0- mole/lit. Dimerization is effectedat temperatures of 0 to l0OC and ethylene pressure of l to 40 atm.

Said objects are also accomplished by the provision of a method ofproducing butene I, wherein, according to the invention. dimerization ofethylene to butene-l is carried out in the presence of a complexorganomctallic catalyst consisting of titanium alcoholates of theformula Ti(OR) and alkylaluminium of the formula AlRf'R', where R is analkyl radical with the number of carbon atoms from 2 to R R or H, R" isthe same as R, in the medium of hydrocarbon solvents such as n-heptane.n-decane, toluene, said catalyst being modified by additives selectedfrom the group consisting of dicyclopentadicnyltitanium dichloride.oxygen, metaphenylenediamine, N-phenyl-B-naphthylamine.

The process of dimerization of ethylene to butene-l by the method of theinvention can also be effected in the presence of such amines asdiethylamine, diisopropylamine, triethylamine, though the yield ofbutene-l in this case materially decreases in spite of the fact that theselectivity of the catalyst is enhanced.

The above-mentioned objects are also accomplished by the provision of amethod of producing butene- Lresiding in that dimerization of ethyleneto butene-l is carried out in the presence of a complex organometalliccatalyst consisting of titanium alcoholates f the formula Ti(OR) andalkylaluminium of the formula AlR "R', where R is an alkyl radical withthe number of carbon atoms from 2 to 4, R'=R or H, R" is the same as R,in the medium of solvents such as ethyl chloride, ethers selected fromthe group consisting of diethyl, vinylbutyl, diphenyl ethers,tetrahydrofuran, a mixture of heptane with ethyl chloride, a mixture ofdiethyl ether with butene-l, a mixture of diethyl ether with ethylchloride.

Dimerization of ethylene to butene-l also take place in the presence ofthe above-mentioned catalysts when dimethyl ether, anisole, phenetole,methyl-butyl ether are used as solvents.

Among the above-cited solvents low-boiling ones are preferable forcarrying out dimerization of ethylene to butene-l (eg, ethyl chloride,diethyl ether), whose boiling point substantially differs from that ofbutene'l. The use of these solvents facilitates heat removal, isolationof butene-l and rectifiction of the solvent.

According to the invention, modifying additives, viz.,dicyclopentadienyltitanium dichloride, oxygen, metaphenylenediamine,N-phenyl-B-naphthylamine, are taken in amounts of O.l5 to 2.0 mole perole of alkylaluminium. The use of dicyclopentadienyltitanium dichloridedoes not change the phase state of the catalyst, sincedicyclopentadienyltitanium dichloride, as well as the other twocomponents of the catalyst, Ti- (OR) and AIR "R', is soluble in thereaction medium and does not form a heterogeneous phase.

Modification of the catalyst Ti(OR) +AlR "R' by additions of oxygenallows a to per cent increase in the yield of butene-l with asimultaneous enhance ment of the process selectivity.

The quantity of oxygen in the reaction vessel is varied within 0.2:l to2:1 with regard to the quantity of alkylaluminium present therein.

The yield of butene-l in the presence of oxygen reaches 342 g per gramof Ti(OC H whereas the best result in the absence of oxygen is 3 l2 gper gram of Ti( OR The content of higher olefines and polyethylene inthe reaction products diminishes from 5.3 to l.7 weight per cent.

Modifiers are introduced into the reaction vessel either prior tofeeding the catalyst, or in the course of the dimerization process. Bestresults are obtained with N-phenyl-B-naphthylamine andmetaphenylenediamine. The application of these compounds as addi tivcswholly suppresses the reaction of polymer formation.

In the herein-proposed method of producing butene l on the catalyst (RO)TiR'. AlR "OR the yield of hutene l per unit weight of the catalyst, ascompared with the known method of producing butene-l (245.6 g per gramof the catalyst) increases by about 25 weight per cent and reaches 312 gper gram of the catalyst. Moreover, while in the known method thequantity of byproducts makes to 25.5 weight per cent, in the presentmethod the respective figure does not exceed 5.3 weight per cent. Thereplacement of the earlier em ployed titanium alcoholate (RO) Ti by thecomplex alcoholate (RO) TiR'-AlR "OR allows an increase in the initialrate of dimerization and an approximately 1.5 times better yield ofbutene-l (from 31.1 g/lit. per hour to 45.7 g/lit. per hour).

Modification of the catalyst Ti(OR) +AlR R' by the above-mentionedadditives allows a 10 to 20 per cent increase in the yield of butene-lwith a simulta' neous enhancement of the process selectivity.

The employment as the reaction medium of such heteroatom-containingsolvents as ethers (diethyl, dimethyl, dibutyl, methylbutyl, diphenyl,divinyl, diallyl ether, tetrahydrofuran) allows an almost ten-foldincrease in the dimerization rate, a raise in the yield of butene-l to2-3 kg per gram of titanium alcoholate, and complete elimination of theformation of butene-2, higher olefines and polyethylene.

When the method of the invention is effected in the medium ofoxygen-containing solvents, the concentration of the catalyst can bevaried within l-lO to 1'10 mole/lit. The molar ratio of the catalystcomponents can also be varied within a wide range (Al/Ti 2.0 2000). Incase oflow molar ratios (Al/Ti less than 2.0) dimerization does not takeplace. When ethylene dimerization is carried out in the medium ofheteroatomcontaining solvents, as the main component of the cata lystuse can be made either of complex titanium alcoholates (RO) TiR"AlR "OR,or of individual titanium alcoholates (OR) Ti.

Bringing down the catalyst concentration to 110 l-l0 mole/liL, with allother things being equal, allows a sharp increase in the catalystefficiency (up to 20000 moles of butene-l per mole of Ti(OR) It has beenestablished that the catalyst in diethyl ether and tetrahydrofuran attemperatures of 20 to 40C does not lose its activity for a period of 48hours. At low temperatures (from -40 to 20C) dimerization of ethylenestarts after a long induction period, this period as such beingconditioned by the reactions of formation of active centres in thesystem Ti(OR) AIR When ethylene is dimerized on (RO) TiR" AlR OR A111,,under otherwise equal conditions, the induction period characterized bythe absence of the ethylene dimerization reaction either diminishes ordisappears.

Within the temperature range of +50 to C the induction period ispractically absent and dimerization starts immediately after blendingthe catalyst compo nents. Best results as to the dimerization rates, theyield of butenel and the catalyst selectively have been obtained whendimerizing ethylene in the medium of diethyl ether. at temperaturesranging from +40 to +80C ethylene pressures ranging from 2 to l2 atm andAl/Ti molar ratios from l to 50. Under said condi tions the rate ofdimerization of ethylene to butene-l with the concentration of Ti(OR),being 0.55 mmole/- lit. reaches 10 g/lit. per minute. the yield ofbutene-l is 2500 g per gram of Ti(OR) and by-products, i.e.,polyethylene, butenes-2 and higher olefines are absent altogether.

Similar results have been obtained when using as the reaction mediummixtures of heteroatom-containing organic compounds with hydroacarbonsof their chlorine-containing derivatives, such as diethyl etherbutene-l; diethyl ether n-heptane, diethyl ether ethyl chloride,tctrahydrofuran ethyl chloride, etc.

Given hereinbelow is a description of the preferred embodiment of themethod of the invention.

Dimerization of ethylene to butene-l (unless otherwise specified) wascarried out in a steel temperaturecontrolled reactor equipped with astirrer provided with a screened drive. With the aid of said stirrer thereaction mass was intensively stirred (with a speed of about 1500r.p.m.). Before the experiments the apparatus was heated to 60C and airwas evacuated from it by means of a vacuum pump to a pressure below 10mm Hg for l hour, after which the apparatus was blown with ethylene.This done, 0.2 lit. of diethyl ether was fed into the reactor, a presettemperature, namely, +40C, was established in it, and ethylene was fedinto the reactor in such an amount as to ensure that required ethylenepressure, namely, 8.0 atm. Then 0.1937 g of alcoholate (C H O);,TiCH,,*Al(c H OC,H,, and 3.05 g of triethylaluminiurn (Al/Ti 49.5) wereintroduced into the reactor. Dimerization of ethylene to butcne-l, whichcommenced immediately upon introducing of 3.05 g of triethylalulminium,was carried out under consntant pressure, this being attained bycontinuously feeding ethylene into the reac tor from a gas bottle. Theprocess was run for 250 minutes till the reactor was completely filledwith butenel. The reaction of ethylene dimerization to butene-l wasinterrupted by adding 20 ml of ethyl alcohol into the reactor. Theresultant butene-l together with the solvent and catalyst weredischarged from the reactor through its bottom valve into the still of arectification column. 445 g of butene-l were produced. The average rateof dimerization of ethylene to butene-l was 8.52 g/lit. per minute, theyield was 2330 g of butene-l per gram of Ti(OC ,H,,) this correspondingto 14150 mole of butene l per mole of Ti(OChd 4H Chromatographicanalysis of the raction products showed absence of polyethylene,butenes-2 and higher olefines.

Other features and advantages of the hereinproposed method of producingbutene-l will become apparent from the following detailed description ofspecific examples illustrating the embodiment thereof.

EXAMPLE I A steel 250 ml capacity reactor equipped with a pro pellcrstirrer (1400 r.p.m.) is charged with l00 ml of hcptane, 3.510" mole of(C H O);;TiC H 'Al(C H 2(OC,H9 the reactor is heated to 40C and thenfilled with ethylene to a pressure of 10 atm, whereupon 510" mole ofAl(C H,,);, is injected into it.

The dimeri ation reaction is run for two hours at the above-statedconstant pressure of ethylene and then terminated by introducing 10 mlof ethyl alcohol into the reactor. The content of higher olefines isdeter mined chromatographically, the polymer is washed with ethylalcohol and dried to constant weight.

49.5 g of butene1, 1.5 g of higher olelines and 1.3 g of the polymer areobtained. The yield of butene-l is 3l2 g per gram of the complextitanium alcoholate. The yield of the by-products is 5.3 weight percent.

EXAMPLE 2 By following the procedure outlined in Example 1, dimerizationof ethylene to butene-l is carried out in the medium of n-decane, at atemperature of 20C, ethylene pressure of 2.7 atm, for a period of 96min. The resulting product contains 18 g of butene-l. The content ofbutene-l, higher olefines and polymer in the resulting product is 97.5,1.9 and 0.6 weight per cent respectively.

EXAMPLE 3 Under the conditions of Example 2, (C H 0 )Il iC- H 'Al(C H(OC H is used as titanium alcohol-ate. In 120 minutes a product isobtained containing 22 g of butene-l. The content of butene-l, higherolefines and polymer in the product is 96.3, 2.8 and 0.9 weight per centrespectively.

EXAMPLE 4 A glass reactor having a capacity of 50 ml and equipped with amagnetic stirrer is charged with 20 ml of n-heptane, 0.ll0 mole of (CH,,()) -,TiC H 'Al(C H (OC H ethylene pressure of 0.55 atm isestablished in it, and at a temperature of 22C 0.38-10 mole of Al(C Hr,) is added.

The initial dimerization rate is 45.7 g/lit. per hour.

EXAMPLE 5 Under the conditions of Example 4,Ti(OC H,,) is used.

The initial rate of ethylene dimerization is 3l.l g/lit. per hour.

EXAMPLE 6 EXAMPLE 7 Under the conditions of Example 6, Ti(OCH C H L, isused. 8 g ofa product are obtained, wherein butene-l makes 88 weight percent, higher olefines and polymer, 12 weight per cent.

EXAMPLE 8 A steel reactor having a capacity of 250 ml is charged with 89ml of ethyl chloride. 5'10" mole of Ti(OCJ-I and 2.510 mole of (C -,HTiCl.

A pressure of 3 atm is established in the reactor and 510 mole of Al(C His introduced thereinto at a temperature of 30C. The reaction is run for90 min.

and gives 44.2 g of butene-l, and 0.8 g of higher olefines and polymer.The yield of butene-l is 260 g per gram of TilOC H that of higherolefines and poly ethylene is 1.78 weight per cent.

EXAMPLE 9 Under the conditions similar to those of Example 8 the amountof (C H l TiClcharged into the reactor is 1210" mole. After a period of90 min. 47 g of butenc- 1 and 0.9 g of higher olefines and polymer areobtained. The yield of butene-l is 276 g per gram of Ti- (OC H the yieldof the by-products making 1.87 weight per cent.

EXAMPLE 10 Under the conditions of Example 8 the amount of (C H l TiClcharged into the reactor is 510 mole. The reaction lasting for 90 min.gives 32 g of butene-l and 0.7 g of higher olevines and polymer. Theyield of b butene-l is 187 g per gram of Ti(OC H that of byproducts is2.14 weight per cent.

EXAMPLE 1 l A steel reactor having a capacity of 250 ml is charged with100 ml of ethyl chloride and ethylene is fed into the reactor at atemperature of 20C to a pressure of 3 atm. Then 5'l0 mole of Ti(OC H5'10" mole of AllC H l and 510" mole of oxygen are introduced into thereactor. The reaction is run for 240 minutes and gives 58 g of butenel0.46 g of higher olefines and 0.53 g of polyethylene. The yield ofbutene-l is 342 g per gram of Ti(OC H and the total yield of byproductsis l.7 weight per cent.

EXAMPLE 12 A reactor similar to that of Example 11 is charged with 100ml of n-heptane, 2'10" mole of Ti(OC H 2'10 mole of AKC H J and 110 moleof oxygen. The reaction run for 186 min. gives 20.4 g of butene-l, 0.35g of higher olefines and 0.42 g of polymer. The yield of butenel is 234g per gram of Ti(C Hq) and the total yield of by-products is 3.7 weightper cent.

EXAMPLE 13 A reactor similar to that of Example 11 is charged with 100ml of toluene, '10" mole of Ti(OC,H,,) 510'" mole of A](C H mole ofoxygen. The result is 21 g of butene-l and 2.9 weight per cent ofbyproducts.

EXAMPLE 14 The conditions are the same as in Example 1 Lexcept that theamount of oxygen charged in the reactor is 1.010 mole and the ethylenepressure established is 6.9 atm. The reaction run for 100 min. gives 31g of butenel. The content of higher olefines and polyethylene in thereaction products is 1.5 weight per cent.

EXAMPLE 15 Under the conditions of Example 13 no oxygen is added intothe reactor. The reaction time is 240 min..

with the resuslt of 33.4 g of butene-l and 1,25 g of higher olefines andpolyethylene. The yield of butene-l is 197 g per gram of Ti(OC H or 96.4weight per cent.

EXAMPLE 16 A steel reactor of a 400 ml capacity is charged with 100 mlof n-heptane, 0.27 g of metaphenylenediamine. 5'10" mole of Ti(OC H and5-10 mole of A|(c H The molar ratio of Al(C H to metaphenylenediamine is2: 1. At a pressure of ethylene of3 atm and at a temperature of 20C,during a period of 280 min. 44 g of butene-l and 0.6 g of higherolefines are obtained. No polymere is detected in the reaction products.The yield of butene-l is 260 g per gram of Ti- (OC H M, or 98.55 weightper cent.

EXAMPLE 17 Under the conditions of Example 16 the molar ratio ofAl(C2H5);; to metaphenylenediamine is l :1. During min. 7 g of butene-land 0.1 g of higher olefines are obtained. Polyethylene is not detectedin the reaction products.

EXAMPLE 18 Under the conditions of Example 16, the molar ratio of Al(C Hto metaphenylenediamine is 10:1. During 90 min. the reaction gives 9.5 gof butene-l, 0.18 g of higher olefines and traces of polymer.

EXAMPLE 19 Under the conditions of Example 16, 0.525 g ofN-phenyl-B-naphthylamine is employed. During 90 min. 17 g of butene-land 0.22 g of higher olefines are obtained. Polymer is absent.

EXAMPLE 20 Under the conditions of Example 17, used is made ofdiisopropylamine. The result is 16.8 g of butenel. 0.25 g of higheroleflnes. and traces of polymer.

EXAMPLE 21 Under the conditions of Example 17, diethylamine is employed.16.3 of butened, 0.2 g of higher olefines, and traces of polymer areobtained.

EXAMPLE 22 Under the conditions of Example 17, 1-10 mole oftriethylamine is employed. With the molar ratio of Al(C H to N(C H P,)equal to 5.1, 11 g of butene-l. 0.1 g of higher olefines, and 0.06 g ofpolymer are obtained.

EXAMPLE 23 A steel reactor having a capacity of 250 ml is charged with84 ml of ethyl chloride, 16 ml of heptane, 5-10 mole of Ti(OC.,H. C HAl(C H (OC H and 9-10 mole of Al(C H At a constant pressure of ethylenemaintained at 57 atm and at a temperature of 20C 23 g of butene-l and0.1 g of solid polyethylene are obtained during 97 min. Content ofbutane in the gaseous phase is about 1 per cent.

Example 24 Under the conditions of Example 23 toluene is used as thesolvent and ethylene pressure is 6.9 atm. During 96 min. 17.5 of buteneland 0.3 g of polyethylene are obtained. The content of butene-l in thegas mixture is 97 per cent, that of butane and higher olefines, 3 percent.

EXAMPLE 25 A steel reactor having a capacity of 250 ml is charged with87.5 ml of ethyl chloride, 10 4 mole of Ti- [()c,H 5'10 mole ofAl(C;,H,-,) At ethylene pressure of 6.9 atm 23 g ofbutene-l are obtainedduring 97 min. The content of butene-l in the gas mixture is 98.5 percent, that of butane and higher olefines, 1.5per

cent.

EXAMPLE 26 A steel reactor having a capacity of 250 ml is charged with90 m1 of ethyl chloride. ml of n-heptane, 5'10 mole of Ti(iso-C H O)5'10 mole of Al(C h At C and ethylene pressure of 27 atm during 70 min.4.55 g of butene-l are obtained, this corresponding to 98.5 weight percent.

EXAMPLE 27 A steel reactor having a capacity of 1000 ml is charged with200 ml of diethyl ether, 0.6 g of Ti- (OC H and 0.2 g of Al(C H 30minutes later another 1.8 g of Al(C H is added into the reactor. Theethylene pressure established in the reactor is 8.0 atm. At 40C during 4hours 151 g of butene-l are obtained. The average dimerization rate is5.25 g/lit. per minute, or 385 moles of butene-l per mole of Ti(OC H perhour. With the experiment being continued after 16 hours. another 175 gof butene-b l are obtained during 110 minutes under the same conditions,with the dimcrization rate 7.9 g/lit. per minute. The total yield ofbutene-l is 547 g per gram of Ti(OC H which makes 3320 moles of butenelper mole of Ti- (OC,H Butenes-Z, higher olefines and polyethylene arenot detected in the reaction products.

EXAMPLE 28 A steel reactor having a capacity of 1000 ml is charged with220 ml of diethyl ether, 0.375 g of tetrabutoxytitanium and 1.245 g oftriethylaluminium (Al/Ti 10.0). At a temperature of +60C and ethylenepressure of 8.0 atm, during 6.5 hours 545 g of hutene-l are obtained.The yield of butene-l is 1500 g per gram of Ti(OC H this correspondingto 8850 moles of butene-l per mole of Ti(Oc ,H,,) 'Cisandtransbutenes-Z, higher oleflnes and polyethylene are absent in thereaction products.

EXAMPLE 29 A steel reactor is charged with 200 ml of diethyl ether,0.1875 g of tetrabutoxytitanium and triethylaluminium in two portions(0.2 g 2.26 g) with an interval of 30 minutes (Al/Ti 39.2). At 60C andethylene pressure of 160 atm 364 g of butene-l are ob tained during 314minutes (the reaction having been stopped 4 hours after the commencementand then the experiment continued with an interval of 16 hours). Theaverage dimerization rate is 5.8 g/lit. per minute, the yield is 11800moles of butene-l per mole of Ti- (OC H or 1940 g of butene-l per gramof Ti- [OC,H No byproducts are detected.

EXAMPLE 30 A reactor is charged with 200 ml of diethyl ether, 0.1875 ofTi(OC.,H,,), and 3.1 l g of triethylaluminium (Al/Ti 49.6). At 40C andethylene pressure of 8.0 atm. during 250 minutes 435 g of butene-l areobtained. The average dimerization rate is 8.5 g/lit. per minute, theyield is 2320 g per gram of Ti(OC H, which corresponds to 14100 moles ofbutene1 per mole of Ti(OC H,,),. The process selectivity is per cent.

EXAMPLE 31 A reactor is charged with 200 m1 of vinylbutyl ether, 5.2 gof tetrabutoxytitanium and 17.2 g of Al(C H During 6 hours at atemperature of 60C and ethylene pressure of 12 atm 40 g of butene-l areobtained.

EXAMPLE 32 A reactor is charged with 200 ml of tetrahydrofuran, 0.36 gof tetrabutoxzytitanium and 5 g of trie thylaluminium. At a temperatureof 60C and ethylene pressure of 12 atm 32 g of butene-l are obtainedduring 10 hours.

EXAMPLE 33 EXAMPLE 34 A reactor is charged with 50 ml of diethyl ether,50 ml of ethyl chloride, 0.17 g of tetrabutoxytitanium and 1.14 g oftriethylaluminum. At a temperature of 60C and ethylene pressure of 8.0atm 6.0 g of butene-l are obtained during 60 minutes. Selectively is 100percent.

EXAMPLE 35 A reactor is charged with 200 ml of diethyl ether, 0.204 g oftetrabutoxytitanium and 10 g of diisobutylaluminium hydride. At atemperature of 60C and ethylene pressure of 73 atm 141 g of butene-l areobtained during 109 minutes. Cis-, trans-butenes-Z, ethylene oligomersand polyethylene are not detected in the reaction products.

EXAMPLE 36 A reactor is charged with 200 ml of diphenyl ether, 0.5 g oftetrabutoxytitanium, and 3.2 g of triethylaluminium (Al/Ti 20). At atemperature of +60C and ethylene pressure of 5.0 atm g of butene-l areobtained during 52.5 minutes. The yield is 300 g of butenel per gram oftetrabutoxytitanium, or 1910 moles of butcne-l per mole of Ti(OC H)hd9),. Selectivity is 100 per cent.

EXAMPLE 37 A reactor is charged with 200 ml of methylphenyl ether(anisole), 0.1875 g of tetrabutoxytitanium and 2.55 g oftriethylaluminium (Al/Ti k= 40). At a temperature of 40C and ethylenepressure of 8.0 atm 307.5 g of butene-l are obtained during 240 minutes.The yield of butene-l is 1640 g per gram of Ti- (OC ,H,,),. Selectivityis 100 per cent.

What is claimed is:

of a solvent selected from the group consisting of ethyl chloride,diethyl ether vinylbutyl ether. methylphenyl ether. diphenyl ether.tetrahydmfuran, a mixture of diethyl ether with butene-l and a mixtureof diethyl ether with ethyl chloride

1. A METHOD OF PREOCUCING BUTENE-1, RESIDING IN THAT ETHYLENE ISDIMERIZED TO BUTENE-1 IN THE PRESENCE OF A COMPLEX ORGANOMETALLICCATALYST CONSITING OF TITANIUM ALCOHOLATES OF THE FORMULA TI(OR)4 ANDALKYLALUMINIUM OF THE FORMULA AIR2"R'', WHERE R IS AN ALKYL RADICAL WITHTHE NUMBER OF CARBON ATOMS FROM 2 TO 4, R''=R OR H AND R" IS THE SAME ASR, IN THE MEDIUM OF A SOLVENT SELECTED FROM THE GROUP CONSISTING OFETHYL CHLORIDE, DIETHYL ETHER, CINYLBUTYL ETHER, METHYLPHENYL ETHER,DIPHENYL ETHER, TETRAHYDROFURAN, A MIXTURE OF DIETHYL ETHER WITHBUTENE-1 AND A MIXTURE OF DIETHYL ETHER WITH ETHYL CHLORIDE.